Fungicidal compositions and methods of combatting fungi using substituted isoindolines

ABSTRACT

Chemical compositions of the formula   WHEREIN EACH R is selected from the group consisting of hydrogen and alkyl; A forms a substituted or unsubstituted hydrocarbon ring of six carbon atoms wherein the substituents are selected from the group consisting of alkyl, alkenyl, halogen, haloalkyl, alkoxy, nitro, and dialkylamino; m is an integer from 1 to 3; n is an integer from 0 to 1; and m + m is an integer from 2 to 3. A fungicidal composition comprising an inert carrier and, as an essential active ingredient, in a quantity toxic to fungi, a compound of the above description. A method for the control of fungi which comprises applying to said fungi a fungicidal composition comprising an inert carrier and, in a quantity toxic to fungi a compound heretofore described.

i United States Patent [191 Richter et al.

[4 1 Nov. 4, 1975 [75] Inventors: Sidney B. Richter, Chicago; Alfred A.Levin, Skokie, both of Ill.

[73] Assignee: Velsical Chemical Corporation, Chicago, Ill.

22 Filed: Mar. 21, 1974 21 Appl. No.: 453,250

Related US. Application Data [62] Division of Ser. No. 297,533, Oct. 13,1972, Pat. No. 3,839,577, which is a division of Ser. No. 176,771, July26, 1971, which is a division of Ser. No. 732,822, May 29, 1968,abandoned.

[52] US. Cl 424/274; 260/326.1 [51] Int. Cl A0ln 9/22 [58] Field ofSearch 260/326.1; 424/274 [56] References Cited UNITED STATES PATENTS3,576,001 4/1971 Bell ct a1 260/326.12

Primary Examiner-Jerome D. Goldberg Assistant ExaminerAllen J. RobinsonAttorney, Agent, or Firm- Robert J. Schwarz; Dietmar H. Olesch [57]ABSTRACT Chemical compositions of the formula (CI-I 2)::

wherein each R is selected from the group consisting of hydrogen andalkyl; A forms a substituted or unsubstituted hydrocarbon ring of sixcarbon atoms wherein the substituents are selected from the groupconsisting of alkyl, alkenyl, halogen, haloalkyl, alkoxy, nitro, anddialkylamino; m is an integer from 1 to 3; n is an integer from 0 to 1;and m+n is an integer from 2 to 3. A fungicidal composition comprisingan inert carrier and, as an essential active ingredient, in a quantitytoxic to fungi, a compound of the above description. A method for thecontrol of fungi which comprises applying to said fungi a fungicidalcomposition comprising an inert carrier and, in a quantity toxic tofungi a compound heretofore described.

4 Claims, No Drawings FUNGICIDAL COMPOSITIONS AND METHODS OF COMBATTINGFUNGI USING SUBSTITUTED ISOINDOLINES This application is a division ofapplication Ser. No. 297,533 filed Oct. 13, 1972; now US. Pat. No.3,839,577 issued 10-1-74, which is a division of Ser. No. 176,771 filedJuly 26, 1971, which is a division of Ser. No. 732,822 filed May 29,1968, now abandoned.

This invention relates to new chemical compositions of matter. Moreparticularly this invention relates to new pesticidally activeheterocyclic compounds of the formula wherein each R is selected fromthe group consisting of hydrogen and alkyl; A forms a substituted orunsubstituted hydrocarbon ring of six carbon atoms wherein thesubstituents are selected from the group consisting of alkyl, alkenyl,halogen, haloalkyl, alkoxy, nitro and dialkylamino; m is an integer from1 to 3; n is an integer from to l; and m n is an integer from 2 to 3.

In a preferred embodiment of this invention each R is selected from thegroup consisting of hydrogen and lower alkyl; A forms a substituted orunsubstituted hydrocarbon ring having a maximum of four substituentswherein the substituents are selected from the group consisting of loweralkyl, lower alkenyl, chlorine, bromine, lower chloroalkyl, lowerbromoalkyl and lower fluoroalkyl, lower alkoxy, nitro and di(loweralkyl) amino.

Exemplary of compounds within the scope of the present invention whichare of particular interest are compounds having the following structuralformulas:

v(II

wherein X,, X X and X, are independently selected from the groupconsisting of hydrogen, alkyl, alkenyl, halogen, haloalkyl, alkoxy,nitro and dialkylamino, and R is as heretofore described.

The compounds of the present invention are unexpectedly useful aspesticides and particularly as fungicides.

The new compounds of the present invention can be prepared fromcompounds having the following formula wherein R, A, m and n are asheretofore described, by reaction with sodium thiocyanate or potassiumthiocyanate. This reaction can be readily effected by combining acompound of Formula V1 with a described thiocyanate in an inert organicsolvent such as ethanol. This reaction usually requires heating andoften reflux temperatures of the reaction mixtures are desirable. Torecover the desired product after completion of the reaction, thereaction mixture can be first filtered to remove any inorganic saltswhich have formed and then stripped of solvent by evaporation,distillation or the like. The resulting product can be used as such orcan be furhter purified if desired by washing, triturating',crystallization and the like if the product is asolid or if the productis a liquid by extraction, distillation, chromatography or other commontechniques employed in the art.

Exemplary of the compound of Formula II which are suitable for preparingthe new compounds of the pres ent invention are1-(a-chloroacety1)indoline, 2-(achloroacetyl)-isoindoline, 2-(a-chloroacetyl 1 ,2,3,4- tetrahydroisoquinoline, 2-( a-chloroacetyl l,2,3 ,4 tetrah ydroisoquinoline 1-( zit-chloroacetyl )-4-chloroindoline, l-(a-chloroacetyl)-3-methylindoline, 1-( a-chloroacetyl)-2-methyl-5-nitroindoline, l-( achloroacetyl )-5-nitroindoline, l-(a-chloroacetyl )-7- bromo-S-nitroindoline, l-( a-chloroacetyl)-6-methoxyindoline, 2-( a-chloroacetyl l methylisoindoline, 2-(a-chloroacetyl 1 -methyll,2,3,4-tetrahydroisoquinoline,l-(a-chloroacetyl)-6- methoxy- 1 ,2,3 ,4-tetrahydroquinoline,l-(achloroacetyl)-6,8-dimethyl 1 ,2,3,4- tetrahydroquinoline, 2-(a-chloroacetyl )-7-nitro- 1,2 ,3 .4-tetrahydroisoquinoline, l-(a-chloroacetyl decahydroquinoline,l-(a-chloroacetyl)-3a,4,7,7a-tetrahydroindoline,l-(a-chloroacetyl)-2-methyl-hexahydroindoline and the like.

The compounds of Formula Vl can be prepared from compounds of thefollowing formula N-II (VII) wherein R, A m and n are as heretoforedescribed, by

reaction with chloroacetyl chloride. This reaction can be readilyeffected by adding the chloroacetyl chloride to a solution of a compoundof Formula VII in a suitable inert organic solvent such as benzene. Inmany instances this reaction is exothermic and cooling of the reactionmixture or a slow controlled addition of the chloroacetyl chloride canbe desirable. The presence of an acid scavenger such as a tertiary aminein the reaction medium is preferred in order to remove the hydrogenchloride which is formed. After the completion of the reaction thedesired product can be recovered by first filtering the reaction mixtureto remove any insolubles which have formed such as amine hydrochloridewhen a tertiary amine is used as an acid scavenger, and thereafterevaporating the solvent used. The remaining product can then be used assuch or can be further purified by distillation if a liquid or byrecrystallization if a solid.

Exemplary compounds of Formula Vll suitable for preparing the compoundsof Formula VI are indoline, isoindoline, 1,2,3,4-tetrahydroquinoline,1,2,3 ,4- tetrahydroisoquinoline, 4-chloroindoline, 3- methylindoline,2-methyl-5-nitroindoline, 7-bromo-5- nitroindoline,2,3-dimethylindoline,

methoxyindoline, 6-methoxyindoline, 6-ethyl-2,3- dimethylindoline,l-methylisoindoline, lbutylisoindoline, l-methyll ,2,3 ,4-

S-methoxy-l ,2,3,4- 3-methyl-1,2,3,4-

tetrah yd roisoquinoline tetrahydroisoquinoline tetrahydroquinoline,6-methyl- 1 ,2,3,4- tetrahydroquinoline, 6,8-dimethyll ,2,3 ,4-tetrahydroquinoline, 6-methoxy-1,2,3,4-

tetrahydroquinoline, 7-nitrol ,2,3 ,4-

tetrahydroisoquinoline, l-methyl-S-nitro- 1 ,2,3,4-tetrahydroisoquinoline, 4,5-dihydroindoline, 5,6- dihydroindoline,3a,4,7,7a-tetrahydroindoline, hexahydroindoline,3a,4,7,7a-tetrahydroisoindoline, 3a, 4,5 ,6-tetrahydroisoindoline,hexahydroisoindoline, l,- 2,3,4,5,S-hexahydroisoquinoline, 1,2,3,4,5,6,7,8- octahydroisoquinoline, l ,2,3 ,4,5 ,8-hexahydro-6-methoxyisoquinoline, 1-methyldecahydroisoquinoline,1,2,3,4,4a,5,6,7-octahydroquinoline, l,2,3,4,5,6,7,8- octahydroquinolineand the like.

The manner in which the compounds of the present invention can beprepared readily is further illustrated in the following examples:

EXAMPLE 1 Preparation of l-(a-Thiocyanoacetyl)lndolinel-(a-ChIoroacetyDindoline 19.6 grams; 0.1 mol), potassium thiocyanate(18 grams; 0.2 mol) and ethanol ml.) were charged into a glass reactionflask equipped with stirrer and reflux condenser. The reaction mixturewas heated at reflux for a period of about 4 hours. After this time themixture was cooled and filtered. The filtrate was evaporated underreduced pressure to yield a brown solid as a residue. The residue waswashed with water and dried. The dried product was then recrystallizedfrom a benzene-pentane mixture to yield 1-( a-thiocyanoacetyl)indolinehaving a melting point of to 127 C. and having the following elementalanalysis as calculated for C H N OS c 1-1 N s- Theoretical 60.58 4.6212.84 14.69 Found 6|.O7 4.64 12.71 14.32

EXAMPLE 2 Preparation of 2-(a-Chloroacetyl)lsoindoline A solution ofisoindoline (60 grams; 0.5 mol) and triethylamine (50 grams) in benzene1,000 ml) is placed in a glass reaction flask equipped with mechanicalstir rer and reflux condenser. Chloroacetyl chloride (56.5 grams; 0.5mol) is slowly added with stirring, over a period of about 20 minutes.The mixture is stirred for an additional period of about 30 minutes andis then filtered. The filtrate is then stripped of benzene to yield 2-(tit-chloroacetyl)isoindoline.

EXAMPLE 3 EXAMPLE 4 Preparation of 1 a-Chloroacetyl)- l,2,3,4-tetrahydroquinoline A solution of l,2,3,4-tetrahydroquinoline (66.5grams; 0.5 mol) and triethylamine (50 grams) in benzene (1,000 ml) wasplaced in a glass reaction flask equipped with mechanical stirrer andreflux condenser. Chloroacetyl chloride (56.5 grams; 0.5 mol) was slowlyadded with stirring over a period of about 15 minutes. An exotherm wasobserved. The mixture was then stirred for an additional period of about15 minutes, was cooled and then filtered. The filtered benzene solutionwas then stripped of solvent resulting in a dark colored oil. The oilwas distilled under reduced pressure to yield l-(a-chloroacetyl)-1,2,3,4- tetrahydroquinoline as a yellow oil having a boiling point of170 to 173 C. at 3.5 mm of Hg pressure and a refractive index of 1.5865at 25 C.

EXAMPLE 5 Preparation of tetrahydroquinoline 1-( a-Chloroacetyl)-l,2,3,4-tetrahydroquinoline (20.9 grams; 0.] mol), potassium thiocyanate(18 grams; 0.2 mol) ethanol (100 ml.) and a few crystals of sodiumiodide were charged into a glass reaction vessel equipped with amechanical stirrer and reflux condenser. The reaction mixture was heatedat reflux for a period of about 7 hours. After this time the mixture wascooled and filtered. The filtrate was poured into cold water resultingin the formation of a white solid. The solid was dissolved in ether andthe etheral solution dried over anhydrous magnesium sulfate andfiltered. The dried solution was then stripped of ether to yield ayellow solid. The solid was dried in vacuo and recrystallized from etherto yield 1-( ath'o cyanoacetyl)-l,2,3,4-tetrahydroquinoline having amelting point of 7374.5 C. and having the following elemental analysisas calculated for C H N OS l-( a-Thiocyanoacetyl)-l ,2,3 ,4-

tetrahydroisoquinoline A solution of 1,2,3,4-tetrahydroisoquinoline(66.5 grams; 0.5 mol) and triethylamine (50 grams; 0.5 mol) in benzene(l l.) was charged into a glass reaction vessel equipped with a stirrer,reflux condenser and addition funnel. Chloroacetyl chloride (56.5 grams;0.5 mol) was slowly added over a period of about 15 minutes. An exothermwas observed. Stirring was continued for an additional 15 minutes afterwhich the reaction mixture was cooled and filtered. The filtrate wasstripped of benzene under reduced pressure resulting in a dark coloredoil as a residue. The dark oil was distilled in vacuo to yield2-(a-chloroacetyl)-l ,2,3,4- tetrahydroisoquinoline as a yellow oilhaving a boiling point of 190 to 195 C. at 7 mm of Hg pressure, and anindex of refraction at 27 C. of 1.5813.

EXAMPLE 7 Preparation of 2-( a-Thiocyanoacetyl l ,2,3 ,4-tetrahydroisoquinoline 2-( a-Chloroacetyl)-l,2,3,4-tetrahydroisoquinoline (13 grams; 0.06 mol), potassiumthiocyanate (l 1 grams), ethanol ml.) and a few crystals of sodiumiodide were charged into a glass reaction flask equipped with stirrerand reflux condenser. The reaction mixture was heated, with stirring,for a period of about 2 hours. After this time the reaction mixture wascooled and filtered. The filtrate was poured into 1,600 ml. of coldwater resulting in the formation of an oil. The oil solidified uponstanding. The solid was recovered by filtration and dissolved in ether.The etheral solution was dried over anhydrous magnesium sulfate, wasfiltered and evaporated to yield a yellow solid. The solid wasrecrystallized from ether to yield 2-(athiocyano)-1,2,3,4-tetrahydroisoquinoline having a melting point of 73to 74 C. and having the following elemental analysis as calculated for CI-1 N 08:

H N S Theoretical 62.04 5.21 12.06 13.80 Found 61.56 5.11 12.00 13.20

EXAMPLE 8 Preparation of l-(a-Chloroacetyl)-4-chloroindoline A solutionof 4-chloroindoline (77 grams; 0.5 mol) and triethylamine (50 grams) inbenzene 1,000 ml.) is placed in a glass reaction flask equipped withmechanical stirrer and reflux condenser. Chloroacetyl chloride (56.5grams; 0.5 mol) is slowly added, with stirring, over a period of about20 minutes. The mixture is stirred for an additional period of about 30minutes and is then filtered. The filtrate is then stripped of benzeneto leave an oil as a residue. The oil is distilled under reducedpressure to yield 1-(a-chloroacetyl)-4- chloroindoline.

EXAMPLE9 Preparation of l-( a-Thiocyanoacetyl )-4- chloroindolineEXAMPLE 10 Preparation of l-( a-Chloroacetyl )-6,8-dimethyll ,2,3,4-tetrahydroquinoline A solution of 6,8-dimethyl-1,2,3,4-

tetrahydroquinoline (84 grams; 0.5 mol) and triethylamine (50 grams) inbenzene (100 ml) is placed in a glass reaction flask equipped withstirrer, reflux condenser and addition funnel. Chloroacetyl chloride(56.5 grams; 0.5 mol) is slowly added, with stirring over a period ofabout 30 minutes. The mixture is stirred for an additional period ofabout 30 minutes and is then filtered. The filtrate is stripped ofbenzene to yield l-(a-chloroacetyl)-6,8-dimethyl-1,2,3,4-tetrahydroquinoline as a residue.

EXAMPLE 1 1 Preparation of l-(a-Thiocyanoacetyl)-6,8-dimethyll ,2,3,4-tetrahydroquinoline 1-( a-Chloroacetyl)-6,8-dimethyl- 1 ,2,3,4-tetrahydroquinoline (24 grams; 0.1 mol), potassium thiocyanate (18grams; 0.2 mol), ethanol (1,000 ml.) and a few crystals of sodium iodideare charged into a glass reaction flask equipped with a mechanicalstirrer and reflux condenser. The reaction mixture is heated at refluxfor a period of about hours. After this time the reaction mixture iscooled and filtered. The filtrate is stripped of solvent and theresulting residue is washed with water and is then recrystallized toyield l-( athiocyanoacetyl)-6,8-dimethyl-1,2,3 ,4- tetrahydroquinoline.

EXAMPLE 12 Preparation of 1-( a-Chloroacetyl) Decahydroquinoline Asolution of decahydroquinoline (21 grams; 0.15 mol) and a triethylamine(15 grams) in benzene (250 ml.) was charged into a 500 ml glass reactionflask equipped with mechanical stirrer, reflux condenser and additionfunnel. Chloroacetyl chloride (18 grams; 0. 15 mol) was slowly added,with stirring, over a period of about minutes. After the addition wascompleted stirring was continued for a period of about minutes. Afterthis time the reaction mixture was filtered to remove the triethylaminehydrochloride which had formed. The filtered solution was then washedtwice with 250 ml portions of dilute hydrochloric acid and then withwater, and thereafter dried over anhydrous magnesium sulfate. The driedsolution was filtered and stripped of benzene under reduced pressure toyield an oil. The oil was distilled twice under reduced pressure toyield l-(a-chloroacetyl) decahydroquinoline as a yellow oil having aboiling point of 143 to 146 C. at 0.3 mm Hg pressure, a refractive indexof 1.5212 at 25 C. and having the following elemental analysis ascalculated for C H CINO:

C H C1 N Theoretical, 61.24 8.41 16.44 6.49 Found, 60.95 8.46 1 .49 6.48

EXAMPLE 13 Preparation of 1-(a-Thiocyanoacetyl) Decahydroquinolinel-(a-Chloroacetyl) decahydroquinoline (5 grams; 0.023 mol), potassiumthiocyanate (4.2 grams; 0.05 mol) and ethanol (50 ml) were charged intoa glass reaction flask equipped with mechanical stirrer and refluxcondenser. The reaction mixture was stirred at reflux, with stirring,for a period of about 2 hours. After this time, the reaction mixture wascooled, filtered and poured into a large volume of cold water to yieldan oil. The oil was extracted with ether and the etheral solution waswashed with water and dried over anhydrous magnesium sulfate. The driedsolution was filtered and stripped of solvent on a steam bath to yield adark oil.

C H N S Theoretical, 60.46 7.61 1 1.76 13.45 Found, 61.14 7.98 11.8713.21

Other compounds within the scope of this invention can be prepared bythe procedures described in the foregoing examples. Presented in thefollowing examples are the essential ingredients required to prepare theindicated named compounds according to the procedures heretoforedescribed.

EXAMPLE l4 3-Methylindolene chloroacetyl chloride potassium thiocyanatel-( (24-thiocyanoacetyl )-3- methylindolene.

EXAMPLE l5 2-Methyl-5-nitroindolene chloroacetyl chloride potassiumthiocyanate l-(a-thiocyanoacetyl)-2- methyllS-nitroindolene.

EXAMPLE l6 4-Methoxyindolene chloroacetyl chloride potassium thiocyanatel-(cit-thiocyanoacetyl)-4'-methoxyindolene.

EXAMPLE l7 l-Methyl-l ,2,3,4-tetrahydroisoquinoline chloroacetylchloride potassium thiocyanate 2-(ozthiocyanoacetyl 1 -methyl- 1 ,2,3,4- tetrahydroisoquinoline.

EXAMPLE 18 6-Methoxy- 1 ,2,3 ,4-tetrahydroquinoline chloroacetylchloride potassium thiocyanate l-(athiocyanoacetyl )-6-methoxy-l ,2,3,4- tetrahydroquinoline.

EXAMPLE 19 7-Nitro-l ,2,3,4-tetrahydroisoquinoline chloroacetyl chloridepotassium thiocyanate 2-(athiocyanoacetyl )-7-nitrol ;2,3 ,4-tetrahydroisoquinoline.

EXAMPLE 20 4,5-Dihydroindoline chloroacetyl chloride potassiumthiocyanate l-(a-thiocyanoacetyl)4,5- dihydroindoline.

EXAMPLE 21 3a, 4,7,7a-Tetrahydroindoline chloroacetyl chloride potassiumthiocyanate l-( car-thiocyanoacetyl)- 321,4,7,7a-tetrahydroindoline.

EXAMPLE 22 Hexahydroisoindoline chloroacetyl chloride potassiumthiocyanate 2-( a-thiocyanoacetyl)hexahydroisoindoline.

EXAMPLE 23 l,2,3,4,4a,5,6,7-Octahydroquinoline chloroacetyl chloridepotassium thiocyanate l-(athiocyanoacetyl)-l ,2,3,4,4a,5,6,7-octahydroquinoline.

EXAMPLE 24 1,2,3,4,5,8-Hexahydroisoquinoline chloroacetyl chloridepotassium thiocyanate 2-(athiocyanoacetyl )-l,2,3,4,5,S-hexahydroisoquinoline.

EXAMPLE 25 1,2,3 ,4,5 ,8-Hexahydro--methoxyisoquinoline chloroacetylchloride potassium thiocyanate 2-(athiocyanoacetyl )-l,2,3,4,5,8-hexahydro-6- methoxyisoquinoline.

EXAMPLE 26 l ,2,3 ,4-Tetrahydro-b-dimethylaminoquinoline chloroacetylchloride potassium thiocyanate l-( athiocyanoacetyl )-l,2,3,4-tetrahydro-6- dimethylaminoquinoline.

The new compounds of this invention are fungicidal in their ability tokill, inhibit, or inactivate a fungus so that it does not grow.Practically, these compounds can be used to prevent fungi and molds fromharming cloth, wood, plants, seeds, fruit, animals, or whatever elsethey attack. The fungicidal compounds should preferably be appliedbefore the infection has occurred and certainly before it has progressedvery far.

For practical use as fungicides, the compounds of this invention aregenerally incorporated into fungicidal compositions which comprise aninert carrier and a fungicidally toxic amount of such a compound. Suchfungicidal compositions, which are usually known in the art asformulations, enable the active compound to be applied conveniently tothe site of the fungus infestation in any desired quantity. Thesecompositions can be solids such as dusts, granules, or wettable powders;or they can be liquids such as solutions, aerosols, or emulsifiableconcentrates. i

For example, dusts can be prepared by grinding and blending the activecompound with a solid inert carrier such as the tales, clays, silicas,pyrophyllite, and the like. Granular formulations can be prepared byimpregnating the compound, usually dissolved in a suitable solvent, onto and into granulated carriers such as the attapulgites or thevermiculites, usually of a particle size range of from about 0.3 to 1.5mm. Wettable powders, which can be dispersed in water to any desiredconcentration of the active compound, can be prepared by incorporatingwetting agents into concentrated dust compositions.

In some cases the active compounds are sufficiently soluble in commonorganic solvents such as kerosene or xylene so that they can be useddirectly as solutions in these solvents. Frequently, solutions offungicides can be dispersed under superatmospheric pressure as aerosols.However, preferred liquid fungicidal compositions are emulsifiableconcentrates, which comprise an active compound according to thisinvention and as the inert carrier, a solvent and an emulsifier. SuchEXAMPLE 27 Preparation of a Dust Product of Example I Powdered talc Theabove ingredients are mixed in a mechanical grinder-blender and areground until a homogeneous, freeflowing dust of the desired particlesize is obtained. This dust is suitable for direct application to thesite of the fungus infestation.

The fungicides of this invention can be applied in any manner recognizedby the art. The concentration of the new compounds of this invention inthe fungicidal compositions will vary greatly with the type offormulation and the purpose for which it is designed, but generally thefungicidal compositions will comprise from about 0.05 to about by weightof the active compounds of this invention. In a preferred embodiment ofthisinvention, the fungicidal compositions will comprise from about 5 toabout 75 by weight of the active compound. The compositions can alsocomprise such additional substances as other pesticides, spreaders,adhesives, stickers, fertilizers, activators, synergists, and the like.

The compounds of the present invention are also useful when combinedwith other fungicides in the fungi cidal compositions heretoforedescribed. The other fungicides can comprise from about 5 to about 95 ofthe active ingredients in the fungicidal compositions. Use ofcombinations of these other fungicides with the compounds of the presentinvention provides fungicidal compositions which are more effective incontrolling fungi and often provide results unattainable with separatecompositions of theindividual fungicides. The other fungicides, withwhich the compounds of this invention can be used in the fungicidalcompositions to control fungi, can include fungicides such as 2-aminobutane, bordeaux mixture, ammonium dimethyl dithiocarbamate,benzoyl trimethyl ammonium bromide, cadmium sulfate, captan, chloranil,copper sulfate, cycloheximide, dichlone, 2,4-dichloro6-(2-chloroanilino)-s-triazine, DDT, dichloran, pdimethylaminobenzenediazosodium sulfonate, dinocap, diphenylmercuri 8-hydroxyquinolinate, dodine,ethylmercuric chloride, ferbam, folpet, gliodin, maneb, metham, mezineb,nabam, pentachloronitrobenzene, PMA, phenylmercuric urea, streptomicin,thiram, zineb, ziram, difolatan, PCNB, and the like.

Such fungicides can also be used in the methods and compositions of thisinvention in the form of their esters, amides, and other derivativeswhenever applicable to the particular parent compound.

When the'compounds of this invention are used as agriculturalfungicides, they can be applied to plant foliage, to seeds, to the soil,or to such parts of plants as the fruits themselves. Plants aresusceptible to a great many diseases which cause widespread damage; andamong some of the more important which can be mentioned are late blighton tomato, powdery mildew on cucumber (Erisiphe cichoracearum), cerealleaf rust on wheat (Puccinia rubigo-vera), and such common soil fungi asfusarium wilt (Fusarium oxysporum), the seed rot fungus (Phythiumdebaranum), and the sheath and culm blight (Rhizoctonia solani). The newcompounds of this invention can also be employed as industrialfungicides to control a variety of fungi which attack such materials asadhesives, cork, paints, lacquers, leather, wood, plastics, and textilessuch as cotton and wool.

The quantity of active compound of this invention to be used for gooddisease control will depend on a variety of factors, such as theparticular disease involved, the intensity of the infestation,formulation, weather, type of crop and the like. Thus, while theapplication of only one or two ounces of active compound per acre of acrop may be sufficient to control a light infestation of certain fungi,a pound or more of active compound per acre may be required to control aheavy infestation of a hardy species of fungus.

The fungicidal utility of the compounds of this invention wasillustrated in an experiment carried out for the control of fusariumwilt (Fusarium oxysporum). In this experiment soil was inoculated withthe fungus organism which was growing on wheat lima bean medium for 14days. The inoculated soil was placed in one ounce paper cups, and thesurface drenched with the test chemical, formulated as an aqueousemulsion of an acetone solution, at the indicated rates per four inchacre. After two to four days, the growth of the fungus was measured andrated in comparison with untreated controls. The results of thisexperiment are presented below:

1. A fungicidal composition comprising an inert carrier and afungicidally effective amount of a compound wherein X X X and X areindependently selected from the group consisting of hydrogen, loweralkyl, chlorine, bromine, trifluoromethyl, lower alkoxy and nitroprovided that only one of X X X and X is nitro or tertiary lower alkyland that at least two of X X X and X are hydrogen.

2. The composition of claim 1 wherein the fungicid ally effectivecompound is 2-( a-thiocyanoacetyl)isoindoline. v

3. A method for combatting fungi which comprises applying to said fungior the locus thereof a fungicidally effective amount of a compound l XiH:

wherein X X X and X are independently selected from the group consistingof hydrogen, lower alkyl, chlorine, bromine, trifluoromethyl, loweralkoxy and nitro provided that only one of X X X and X is nitro ortertiary lower alkyl and that at least two of X X X and X are hydrogen.

4. The method of claim 3 wherein the fungicidally effective compound is2-(oz-thiocyanoacetyl)isoindoline l=

1. A FUNGICIDAL COMPOSITION COMPRISING AN INERT CARRIER AND AFUNGICIDALLY EFFECTIVE AMOUNT OF A COMPOUND
 2. The composition of claim1 wherein the fungicidally effective compound is 2-( Alpha-thiocyanoacetyl)isoindoline.
 3. A method for combatting fungi whichcomprises applying to said fungi or the locus thereof a fungicidallyeffective amount of a compound
 4. The method of claim 3 wherein thefungicidally effective compound is 2-( Alpha-thiocyanoacetyl)isoindoline.